DE2757982C2 - Compounds of the isoindoline series and process for the production of pigments with improved application properties - Google Patents

Description

30th

10

15th

in the A for cyano, carbonamido, N-phenyl- or N- (chloropheny]) - carbonamido or one with one Benzene ring condensed unsaturated heterocyclic 5- or 6-membered radical and B for one Remainder of the barbituric acid are available by condensation of l-amino-3-imino-isoindoline with the corresponding Cyanomethylene compound at pH> 7 and then with barbituric acid in the range between pH 1.5 and 3.5 in a liquid reaction medium at temperatures between 20 and 150 ° C, thereby characterized in that the condensation in the presence of water or in water performs

2. The method according to claim 1, characterized in that the condensation is carried out in the presence of water and surfactants.

3. The method according to claim 2, characterized in that that one uses 10 to 100% by weight, based on barbituric acid, of surface-active agents.

4. The method according to claims 2 or 3, characterized in that one is used as the surface-active Medium Ci- to Cs-alkylnaphthalenesulfonic acid, Condensation product of phenol, urea and formaldehyde, addition products of ethylene oxide and / or propylene oxide on C2- to C2o-alkanols, alkanediols, alkanetriols, aliphatic Qo-bis C2o-carboxylic acids and / or their amides, C10- to C2o-fatty alcohols and condensation products Isobutyraldehyde, formaldehyde, and urea are used.

5. Process according to claims 1 to 4, characterized in that the cyanomethylene compound Cyanoacetamide and, as barbituric acid, unsubstituted barbitic acid are used.

6. Isoindoline compound of the formula

HN NH

The invention relates to a process for the production of strongly colored and easily dispersible pigments based on isoindoline.

The invention also relates to 2 new isoindoline compounds, namely compounds of the formulas

NC-C-CN

and

CN

55

60

65

Compounds of the formula

NC-C-A

NH

(D

in the A and B et al. the meaning given later have, and their production are known from DE-OS 16 70748. According to the information on page 9 of the OS is the conversion to the monocondensation product (= 1st stage) in lower alkanols, glycols, Glykolmonoäthem, diglykolmonoäthern, lower Car- ι s In the case of readily water-soluble l-amino-3-imino-isoindolines water or alcohol-water mixtures should be possible as the reaction medium. In these implementations An addition of ammonia-binding agents can be useful, especially if the Starting component contains groups that react with ammonia.

The condensation of the monocondensation product (= 2nd stage) to the biscondensation product takes place preferably in higher boiling solvents.

According to the process of the prior art, the condensation products of the formula I are obtained only in moderate yield and in one for use as a pigment, especially for use in coloring of plastics and paints in the near-pure-tone area, poorly suitable form.

The pigments obtained in this way are difficult to disperse in plastics and are produced accordingly weak coloration. In addition, paints that contain the pigment of the prior art, insufficient light and weather fastness.

The object of the invention was to provide a process for the production of strongly colored and in particular in Plastics to find easily dispersible pigments of formula 1. Another job was to get one To develop processes that reduce the pollution of the wastewater by solvents or

This object is achieved by the process according to the invention. It has been found that an in the application properties improved pigment of the formula

The 5- or 6-membered heterocyclic radical condensed with a benzene nucleus are preferred Benzimidazolyl-2, quinazolyl-2 into consideration

The barbituric acid residues B include those of N-methyl-, N-phenylbarbituric acid, 2-thiobarbituric acid, the 2-imino and 2-N-cyaniminobarbituric acid, unsubstituted barbituric acid or mixtures of the barbituric acids mentioned. For B, the remainder of the barbituric acid is particularly preferred

According to the process of the invention, the pigments of the formula I are obtained directly in a strongly colored and easily dispersible pigment form. Depending on how the reaction is carried out in the 2nd stage, you can do both Produce translucent as well as highly scattering (i.e. highly opaque) pigment forms of I. the Process products result in plastics, especially in thermoplastics such as rigid PVC, Polyethylene, polypropylene, polystyrene, polyacrylate, polymethacrylate, Copolymers of styrene, acrylonitrile, butadiene and / or acrylic acid esters and in soft PVC lightfast, brilliant and strong colorations. In paints, one obtains strong colors in the near-pure shade range lightfast and brilliant colors.

The process according to the invention is carried out in such a way that first l-amino-3-imino-isoindoline, which has been prepared in a known manner, with the equimolar amount of the cyanomethylene compound

, CN

CH,

converts at pH> 7 (level 1). This creates the monocondensation product of the formula

(HIa)

NH

NC-C-A

(HIb)

(D

in which A stands for cyano, carbonanido, N-phenylcarbonamido, N- (chlorophenyl) -carbonamido or an unsaturated heterocyclic 5- or ole-membered radical condensed with a benzene nucleus, and B stands for a radical of barbituric acid, by condensation of 1-amino-3 -iminoisoindoline with the corresponding cyanomethylene compound at pH> 7 and then with barbituric acid in the range between pH 1.5 and 3.5 in a liquid reaction medium at temperatures between 20 and 150 ^° C. if the condensation is obtained in the presence of water or in water performs

corresponds, in pure form. That is, surprisingly, under the reaction conditions no or practically no biscondensation product

The thus obtained monocondensation product of the 1st stage is then with the equimolar amount of Barbituric acid further condenses to pigment I in the range between pH 1.5 and 3.5 (stage 2).

The process can be carried out in such a way that the process product of the 1st stage is isolated and only then carries out the further condensation. The condensations of FIG. 1 are advantageously carried out. 1st and 2nd stage, however, in the same reaction vessel (and in the same reaction medium). Here is after End the monocondensation of the 'pH in the reaction medium to 1.5 to 3.5 by adding Acid set.

The reaction medium used for the process of the invention is organic water-miscible solvents, Mixtures of these solvents with water or, preferably, water are suitable

As solvents are, for. B. to mention: the Ci- bis C4-alkanols such as methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, tert-butanol, C2 bis Gt-alkynediols such as ethylene glycol, 1,2- and 13-propylene glycol, the butanediols, glycol monoalkyl ethers such as monoinethyl, monoethyl, monopropyl or monobutyl ethers of ethylene glycol and diethylene glycol, lower carboxamides such as dimethylformamide, Dimethylacetamide or dimethylpropionic acid amide and cyclic amides such as N-methylpyrrolidone.

The preferred reaction medium is water and a mixture of water with ethylene glycol

The condensation of the 1st stage takes place at pH> 7 after the addition of the compound II in a flat manner Temperatures between 20 and 100, preferably between 40 and 80 ° C.

Advantageously, the reaction mixture is then before or after adding the barbituric acid to a pH between 1.5 and 3.5 adjusted at temperatures between 20 and 150, preferably between 40 and 100 ° C the condensation takes place to I.

The amount of acid can be measured so that the ammonia released during the reaction is bound and is neutralized with it, and thus the pH value is kept between 1.5 and 3.5. Preferably leads the condensation in stage 2 is carried out in such a way that the pH value in the reaction mixture is added by adding acid is maintained within the desired pH range. In this way, the condensation of the 2nd stage can be carried out within a narrow pH range.

As acids come z. B. aliphatic and aromatic carboxylic and / or sulfonic acids. in the individual are z. B. to name:

Formic acid, acetic acid, propionic acid,
Oxalic acid, succinic acid, glutaric acid, citric acid, benzoic acid, phthalic acid,
Salicylic acid, benzenesulfonic acid,
Naphthalenesulfonic acid, phenolsulfonic acid

or mixtures thereof.

In addition, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and sulphurous acids can also be used as acids Acid or mixtures thereof. Mixtures of mineral acids with organic acids can also be used Use carboxylic and / or sulfonic acids.

Since the condensations of the 1st and 2nd stage are specific, the process can also be carried out in this way be that a mixture of the equimolar amount of the cyanomethylene compound (II) and the Barbituric acid - based on l-amino-3-iminoisoindoline - Submit at the beginning and then in the manner indicated above the condensation of the 1st and then of the 2nd stage.

According to this process variant, which is advantageous for the technical implementation of the process, one obtains the process product in the same advantageous pigment form as when the reaction components were added immediately before carrying out the reaction stage.

The condensation can be carried out in the absence or in the presence of surfactants. Since in the latter case particularly easily dispersible, strongly colored pigment forms are obtained, the condensation is preferably carried out in the presence of surface-active agents. The surface-active agent can be added both during the condensation of the 1st stage and before or after the condensation of the 2nd stage. The amount of the surface-active agent or agents used is not critical above a minimum amount and can therefore be varied within wide limits. The lower amount used is about 5% by weight, based on BH2. It is expedient to use 5 to 400% by weight, preferably 10 to 100% by weight, based on the amount of BH _{2 used} .

Suitable surface-active compounds are nonionic, anionic or cationic, which usually used as dispersants, wetting agents and / or protective colloids. As an anionic surface-active come z. B. possible: Ct- to C2o-alkylbenzenesulfonic acids, CU- to C2o-alkylphenolsulfonic acids, Mono- and bis-Ci- to Cio-alkylnaphthalenesulfonic acids, partially sulfonated polystyrene, water-soluble condensation products of jJ-naphthalenesulfonic acid and / or Ci- to Cio-alkylnaphthalene-ß-sulfonic acid and formaldehyde, condensation products of phenolsulfonic acids, formaldehyde and urea, condensation products from phenol, urea, formaldehyde and sodium sulfite, condensation products from phenol-formaldehyde, those with phenol sulfonic acid, urea and formaldehyde have been post-condensed, lignosulfonates, long-chain fatty acids, resin acids in Form of the alkali metal, alkaline earth metal or ammonium salts.

Nonionic surfactants are e.g. B. addition products of ethylene oxide and / or propylene oxide to alkenols, alkanediols, alkane polyols, phenols, carboxylic acids, carboxamides, mono-, di- and Polyamines. Other agents are water-swellable to water-soluble polymers, such as polymers Vinylpyridine, N-vinylpyrrolidone or copolymers from water-soluble monomers such as N-vinylpyrrolidine, Acrylic acid amide and / or acrylic acid with water-insoluble monomers such as acrylonitrile, methacrylic acid ester, Acrylic acid esters, vinyl acetate, vinyl chloride and / or styrene, as well as polyvinyl alcohol, C10 bis C20 fatty alcohols and condensation products from isobutyraldehyde, Formaldehyde and urea.

The surfactants can also be used in the form of mixtures.

Ci- to Cs-alkylnaphthalenesulfonic acid, condensation products of phenol, urea and formaldehyde, addition products of ethylene oxide and / or propylene oxide with C2- to C2o-alkanols, alkanediols, alkanetriols, aliphatic C10- to C20-carboxylic acids and / or their amides are preferred , C10 to C ₂ o fatty alcohols as surface-active agents and condensation products of isobutyraldehyde, formaldehyde and urea.

By suitable choice of the conditions in the implementation of the monocondensation product with the Barbituric acids, the reaction can be controlled so that both a reddish glaze or strong opaque pigment form is obtained or a greenish translucent or highly opaque pigment form. The latter is characterized by particularly good light and weather fastness.

The reddish translucent pigment form is obtained when carrying out the condensation of the 2nd stage in the range between pH 2.5 and 3.5 at a temperature of 60-90 ⁰ C.

The greenish translucent pigment form arises when you see the condensation of the 2nd stage in the area between pH 1.5 and 2.5 at a temperature of 60-90 ° C.

Strongly opaque, red or greenish pigment forms with compared to the dye of DE-OS 16 70 748 is significantly improved light and weather fastness if you carry out the condensation of the 2nd stage under the conditions mentioned above, and that Reaction mixture to end or after the end of the condensation under pressure to 110 to 140 ° C warmed up.

The method according to the invention is additionally explained by the exemplary embodiments. The in The following parts and percentages are based on weight.

example 1

64 parts of o-phthalonitrile are in 400 parts Ethylene glycol suspended and gassed for 3 hours at 60 ° C with 15 parts of ammonia. The resulting solution of the l-amino-3-iminoisoindoline is allowed to form one pH 9, a 60 ° C warm suspension of 64 parts of barbituric acid and 42 parts of cyanoacetamide in 750 parts Run in water and stir at 60 ° C. for 2 hours. Then the reaction mixture is made up with sulfuric acid pH 3 acidified and stirred at pH 3 and 60 ° C for 2 hours. Then 16 parts of oleic acid ethanolamide are added closed, heats to 90 ° C, sucks off and dries. 150 parts of a strongly colored, neutral yellow are obtained Pigments with good dispersibility in plastics.

Example 2

135 parts of approximately 25% ammonia water and 62.2 parts of ethyl cyanoacetate are used for two hours Stirred at room temperature and diluted with 750 parts of water. 64 parts of barbituric acid are introduced and the mixture is heated to 60 ° C, a pH of approx. 9 being established The solution of l-amino-3-imino-isoindoline prepared according to Example 1 is left to this suspension run in and stir for two hours. 40 parts of the sodium salt of a C3 -C4 alkylnaphthalenesulfonic acid are then added the mixture is acidified to pH 3 and stirred for two hours at 60 ° C and three hours at 130 ° C after. After cooling, the product is filtered off with suction, washed and dried. 29 parts of a very strong, lightfast and relatively opaque yellow pigment with good spreadability

50

Example 3

_{42 parts of cyanoacetamide and 15 parts of a Ci 0} -bis CM fatty alcohol mixture are added to the solution of l-amino-3-iminoisoindoline, prepared analogously to the information in Example 1 from 64 parts of o-phthalonitrile in 400 parts of ethylene glycol, diluted with 300 parts of IsobutanGl and stirred at 60 ° C. for two hours. The resulting suspension of the monocondensation product is acidified to pH 2 with sulfuric acid, then 64 parts of barbituric acid are added and so much water that the reaction mixture remains stirrable. 7 and the addition of more water the isobutanol to completion, filtered and dried to give 149 parts of an _i brilliant, deep and wide reiativ greenish yellow pigment having good light fastness and good spreadability

Example 4

The procedure is as in Example 2, but instead of a solution prepared analogously to Example 1, l-Amino-2-iminoisoindoline in solid form or an equivalent amount of a solid addition product of this z. B. with ethylene glycol (DE-PS 8 79100 Example 25) or an equivalent amount of a solid Salt of l-amino-2-iminoisoindoline and a mineral or carboxylic acid.

115 parts of a strongly colored, lightfast product are obtained and relatively opaque, neutral yellow pigment with good spreadability

Example 5

The procedure is as in Example 3, the reaction mixture is heated after the isobutanol has been distilled off after 10 hours to 130 ° C. 130 parts of a highly opaque, brilliant, greenish yellow pigment are obtained with good weather resistance in near-solid lacquer colors.

Example 6

The procedure is as in Example 1, except that 100 parts of formic acid are used for acidification. 150 parts are obtained a strong, neutral yellow pigment with good dispersibility in plastics.

Example 7

The procedure is as in Example 1, except that 16 parts of the reaction mixture are added to pH 3 before acidification a condensation product of phenolsulfonic acid, formaldehyde and urea, stirred for 2 hours 60 ° C and then a further 14 hours at pH 6-7 and 130 ° C. The result is a brilliant, opaque, good lightfast and weatherproof yellow pigment.

Example 8

The procedure is as in Example 3, but instead of barbituric acid, 82 parts of the sodium salt are used N-methyl-barbituric acid. 140 parts of a brilliant, greenish yellow pigment with good Distributability.

Example 9

The procedure is as in Example 8, except that 76 parts of cyaniminobarbituric acid are used. 137 parts are obtained a reddish yellow pigment of high color strength.

Example 10

The procedure is as in Example 3, but working without fatty alcohol and diluting the batch with glycol instead of isobutanol. The resulting suspension of the mono-condensation product is acidified with sulfuric acid to pH 2, then 64 parts of barbituric acid are added and the mixture diluted until glycol that it remains still just stirrable After 'half an hour of stirring at pH 2 and 6O ⁰ C is charged with 700 parts water diluted nnchgerührt further 1.5 hours at 6O ⁰ C and then 10 hours at 130 ° C It erhallt 120 parts of a strongly greenish, opaque yellow pigment having good light and weather fastness

030 20B / 42S

ίο

Example 11

The procedure is as in Example 1, except that 33 parts of malonitrile are used instead of cyanoacetamide. Man contains 120 parts of an easily distributable, neutral yellow pigment.

Example 13

The procedure is as in Example 1, except that 93 parts of 2-cyanomethyl-quinazolone are used instead of cyanoacetamide. 150 parts of a red pigment with good properties are obtained.

Example 12 Example 14

The procedure is as in Example 1, but using. The procedure is as in Example 1, but using

instead of cyanoacetamide 97 parts of p-chloro-cyanacet- ι ο instead of cyanoacetamide 79 parts of 2-cyanomethyl-ben-

anilide. 150 parts of an easily distributable zimidazole are obtained. 150 parts of a yellowish tinge are obtained

Orange pigments with good fastness properties. Red pigment.

Claims (1)

Patent claims: 1. Process for the production of an improved in the application properties Pigment of the formula 7. Isoindoline compound of the formula O